Simplified and traditional chinese, to cover the markets in China, Hong Kong/Macau, and Taiwan. Although the iPhone is not officially offered in China, I'm sure Apple will reach an agreement with China Mobile or China Unicom sooner or later, opening up a potentially enormous market. Persuading people to pay is a different matter, but I can see that happening if they offer a chinese language service.
KT in Korea is also going to be officially offering the iPhone soon. There's another fairly affluent market, so Korean would be worth looking at.
Russian and Brazilian Portugese are also worth considering, as Russia and Brazil are BRIC countries etc.
And has been mentioned, English is a given, and the Japanese have now warmed to the iPhone also, despite earlier predictions.